CN103232412B - One prepares the method for 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid - Google Patents
One prepares the method for 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid Download PDFInfo
- Publication number
- CN103232412B CN103232412B CN201310140958.6A CN201310140958A CN103232412B CN 103232412 B CN103232412 B CN 103232412B CN 201310140958 A CN201310140958 A CN 201310140958A CN 103232412 B CN103232412 B CN 103232412B
- Authority
- CN
- China
- Prior art keywords
- solution
- reaction
- acetonitrile
- thiodiphenylamine
- concentrated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002253 acid Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 111
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims abstract description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000006837 decompression Effects 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000007858 starting material Substances 0.000 abstract 1
- -1 research finds Chemical compound 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229950000688 phenothiazine Drugs 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 201000000980 schizophrenia Diseases 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- KDTWUXOFWMBCBI-UHFFFAOYSA-N 3-butyloxetane-2,4-dione Chemical compound CCCCC1C(=O)OC1=O KDTWUXOFWMBCBI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WLJVNTCWHIRURA-UHFFFAOYSA-N Heptanedioic acid Natural products OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 1
- 206010026749 Mania Diseases 0.000 description 1
- 208000028017 Psychotic disease Diseases 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- YOURXVGYNVXQKT-UHFFFAOYSA-N oxacycloundecane-2,11-dione Chemical compound O=C1CCCCCCCCC(=O)O1 YOURXVGYNVXQKT-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
One prepares the method for 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid, and step is: in reaction vessel, add Amol thiodiphenylamine and Bmol MALEIC ANHYDRIDE, then add acetonitrile; Stir in downhill reaction container and drip concentrated hydrochloric acid, obtain reaction solution, by reaction solution from room temperature to 40 ~ 80 DEG C and stirring reaction 1 ~ 2.5h, obtain mixed solution, wherein A:B=2.5:(2.5 ~ 3.0); Mixed solution decompression is steamed acetonitrile, and obtain concentrated solution, wherein in concentrated solution, the volume of acetonitrile is 15 ~ 20% of acetonitrile volume in mixed solution; Solution to be concentrated adds water after being cooled to room temperature wherein, suction filtration after stirring, and by filter cake washing, drying, obtains 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid.The present invention adopts acetonitrile as solvent, and concentrated hydrochloric acid is catalyzer, and easy and simple to handle, the reaction times is short, mild condition, and aftertreatment is simple, and cheaper starting materials is easy to get, and productive rate is high.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly one prepares the method for 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid.
Background technology
Thiodiphenylamine is a kind of heterogeneous ring compound of nitrogenous, sulphur, be also called sulphur naphthazin(e) or phenothiazine, research finds, thiodiphenylamine and derivative thereof have very high pharmacologically active and biological activity, in recent years, oxidation inhibitor, biological medicine and dyestuff etc. that phenothiazine compound is widely used in stopper, lubricant are industrial, in addition, also can be used for the aspects such as synthetic drugs, fruit tree insecticide, electroluminescent organic material.Along with the continuous exploration discovery of researcher, phenothiazines is applicable to treat acute and chronic schizophrenia, mania and other severe psychosis, can control the symptoms such as excitement, attack, illusion and vain hope.Therefore, the research for phenothiazine compound is very meaningful.
PhilipS.Winnek etc. mention in US Patent No. 2461460: mixed with succinyl oxide by thiodiphenylamine, oil bath backflow 16h at 150 DEG C, products therefrom under agitation adds ammonium hydroxide, after filtration, filtrate uses 10% hcl acidifying, solid 75% ethyl alcohol recrystallization.And claim aforesaid method to be applicable to too using Pyroglutaric acid, adipic anhydride, pimelic acid acid anhydride, nonane diacid acid anhydride, sebacic anhydride, butyl-malonic anhydride, methylmalonic acid acid anhydride and MALEIC ANHYDRIDE as acylating agent to synthesize different acylates.The method temperature of reaction is high and the time is longer, and aftertreatment also bothers relatively.
Summary of the invention
The object of the present invention is to provide that a kind of reaction conditions is gentle, easy and simple to handle, the reaction times is short, aftertreatment is simple and the method preparing 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid that productive rate is high.
To achieve these goals, technical scheme of the present invention comprises the following steps:
The first step, adds Amol thiodiphenylamine and Bmol MALEIC ANHYDRIDE, then adds acetonitrile in reaction vessel; Stir in downhill reaction container and drip concentrated hydrochloric acid, obtain reaction solution, by reaction solution from room temperature to 40 ~ 80 DEG C and stirring reaction 1 ~ 2.5h, obtain mixed solution, wherein A:B=2.5:(2.5 ~ 3.0);
Second step, mixed solution decompression is steamed acetonitrile, and obtain concentrated solution, wherein in concentrated solution, the volume of acetonitrile is 15 ~ 20% of acetonitrile volume in mixed solution; Solution to be concentrated adds water after being cooled to room temperature wherein, suction filtration after stirring, and by filter cake washing, drying, obtains 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid.
The consumption of described acetonitrile is CmL, C=(4000 ~ 6000) A.
The mass concentration of described concentrated hydrochloric acid is 36 ~ 38%, and consumption is DmL, D=(60 ~ 100) A.
Stir speed (S.S.) in the described the first step is 1500 ~ 2500r/min.
Heat-up rate in the described the first step is 3 ~ 4 DEG C/min.
In described second step, solution to be concentrated adds XmL water after being cooled to room temperature wherein, X=(4000 ~ 8000) A.
Required time that stirs in described second step is 5 ~ 10min.
Drying in described second step is that room temperature is dried.
Described A:B=2.5:2.75, temperature of reaction is 60 DEG C, and the reaction times is 2h.
Compared with prior art, the present invention has following beneficial effect:
The invention provides the preparation method of a kind of 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid, the method with thiodiphenylamine and MALEIC ANHYDRIDE for raw material, acetonitrile is solvent, concentrated hydrochloric acid is catalyzer, namely prepares 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid in 40 ~ 80 DEG C of reactions.Cheap and easy to get and the excellent catalytic effect of concentrated hydrochloric acid that the present invention uses, raw material of the present invention is easy to get, easy and simple to handle, reaction is easy to control, reaction conditions is gentle and the reaction times is shorter, equipment requirements is low, and aftertreatment is simple and productive rate is high, is a kind of simple, economic method preparing 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid.
Embodiment
The present invention is using acetonitrile as solvent, and concentrated hydrochloric acid is catalyzer, is reacted by reaction solution and generate 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid at 40 ~ 80 DEG C, its reaction formula as the formula (1):
Below in conjunction with the present invention preferably specific embodiment the present invention is described in further detail.
Embodiment 1
The first step, 0.0025mol thiodiphenylamine and 0.0025mol MALEIC ANHYDRIDE is added in the there-necked flask of drying, add 10mL acetonitrile again, the concentrated hydrochloric acid that 0.2mL mass concentration is 36 ~ 38% is slowly dripped in the stirring velocity downhill reaction container of 1500r/min, obtain reaction solution, reaction solution is warming up to 40 DEG C from room temperature with the speed of 3 DEG C/min, and with the speed stirring reaction 2.5h of 1500r/min, obtains mixed solution;
Second step, mixed solution decompression is steamed acetonitrile, obtain concentrated solution, in concentrated solution, the volume of acetonitrile is 15% of acetonitrile volume in mixed solution, solution to be concentrated adds 10mL water after being cooled to room temperature wherein, suction filtration after stirring 5min, dries filter cake washing, room temperature, and the white powder obtained is 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid; Productive rate is 89%.
1H-NMR(CDCl
3，400MHZ)δppm：7.01（d,1H,=CH）,7.47～7.65(m,8H,ArH),7.82(d,1H,=CH),11.67(s,1H,COOH)。
Embodiment 2
The first step, 0.0025mol thiodiphenylamine and 0.0028mol MALEIC ANHYDRIDE is added in the there-necked flask of drying, add 10mL acetonitrile again, the concentrated hydrochloric acid that 0.15mL mass concentration is 36 ~ 38% is slowly dripped in the stirring velocity downhill reaction container of 2200r/min, obtain reaction solution, reaction solution is warming up to 50 DEG C from room temperature with the speed of 4 DEG C/min, and with the speed stirring reaction 2.5h of 2200r/min, obtains mixed solution;
Second step, mixed solution decompression is steamed acetonitrile, obtain concentrated solution, in concentrated solution, the volume of acetonitrile is 20% of acetonitrile volume in mixed solution, solution to be concentrated adds 10mL water after being cooled to room temperature wherein, suction filtration after stirring 5min, dries filter cake washing, room temperature, and the white powder obtained is 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid; Productive rate is 91%.
Embodiment 3
The first step, 0.00250mol thiodiphenylamine and 0.00275mol MALEIC ANHYDRIDE is added in the there-necked flask of drying, add 12mL acetonitrile again, the concentrated hydrochloric acid that 0.2mL mass concentration is 36 ~ 38% is slowly dripped in the stirring velocity downhill reaction container of 1700r/min, obtain reaction solution, reaction solution is warming up to 60 DEG C from room temperature with the speed of 3 DEG C/min, and with the speed stirring reaction 2h of 1700r/min, obtains mixed solution;
Second step, mixed solution decompression is steamed acetonitrile, obtain concentrated solution, in concentrated solution, the volume of acetonitrile is 17% of acetonitrile volume in mixed solution, solution to be concentrated adds 15mL water after being cooled to room temperature wherein, suction filtration after stirring 7min, dries filter cake washing, room temperature, and the white powder obtained is 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid; Productive rate is 95%.
Embodiment 4
The first step, 0.0025mol thiodiphenylamine and 0.0030mol MALEIC ANHYDRIDE is added in the there-necked flask of drying, add 15mL acetonitrile again, the concentrated hydrochloric acid that 0.25mL mass concentration is 36 ~ 38% is slowly dripped in the stirring velocity downhill reaction container of 2100r/min, obtain reaction solution, reaction solution is warming up to 70 DEG C from room temperature with the speed of 4 DEG C/min, and with the speed stirring reaction 1.5h of 2100r/min, obtains mixed solution;
Second step, mixed solution decompression is steamed acetonitrile, obtain concentrated solution, in concentrated solution, the volume of acetonitrile is 20% of acetonitrile volume in mixed solution, solution to be concentrated adds 15mL water after being cooled to room temperature wherein, suction filtration after stirring 7min, dries filter cake washing, room temperature, and the white powder obtained is 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid; Productive rate is 90%.
Embodiment 5
The first step, 0.0025mol thiodiphenylamine and 0.0030mol MALEIC ANHYDRIDE is added in the there-necked flask of drying, add 15mL acetonitrile again, the concentrated hydrochloric acid that 0.2mL mass concentration is 36 ~ 38% is slowly dripped in the stirring velocity downhill reaction container of 2500r/min, obtain reaction solution, reaction solution is warming up to 80 DEG C from room temperature with the speed of 3 DEG C/min, and with the speed stirring reaction 1h of 2500r/min, obtains mixed solution;
Second step, mixed solution decompression is steamed acetonitrile, obtain concentrated solution, in concentrated solution, the volume of acetonitrile is 16% of acetonitrile volume in mixed solution, solution to be concentrated adds 20mL water after being cooled to room temperature wherein, suction filtration after stirring 10min, dries filter cake washing, room temperature, and the white powder obtained is 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid; Productive rate is 87%.
The preparation method of a kind of 4-provided by the invention (N-thiodiphenylamine-)-carbonyl-2-butylene acid, have employed concentrated hydrochloric acid cheap and easy to get as reaction catalyzer and catalytic effect is splendid, be solvent with acetonitrile and in aftertreatment, most of solvent reclaimed, reaction conditions is gentle and the time is short, does not need recrystallization can obtain productive rate and all higher target compound of purity.Can yet be regarded as the preparation method of a kind of easy, economic 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid.
Claims (2)
1. prepare a method for 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid, it is characterized in that, comprise the following steps:
The first step, adds Amol thiodiphenylamine and Bmol MALEIC ANHYDRIDE, then adds CmL acetonitrile in reaction vessel; Stir in downhill reaction container and drip the concentrated hydrochloric acid that DmL mass concentration is 36 ~ 38%, obtain reaction solution, by reaction solution from room temperature to 40 ~ 80 DEG C and stirring reaction 1 ~ 2.5h, obtain mixed solution, wherein A:B=2.5:(2.5 ~ 3.0), C=(4000 ~ 6000) A, D=(60 ~ 100) A, stir speed (S.S.) is 1500 ~ 2500r/min, and heat-up rate is 3 ~ 4 DEG C/min;
Second step, mixed solution decompression is steamed acetonitrile, and obtain concentrated solution, wherein in concentrated solution, the volume of acetonitrile is 15 ~ 20% of acetonitrile volume in mixed solution; Solution to be concentrated adds XmL water after being cooled to room temperature wherein, X:A=(4000 ~ 8000): 1, stir 5 ~ 10min to stirring, then suction filtration, filter cake washing, room temperature are dried, obtains 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid.
2. the method preparing 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid according to claim 1, it is characterized in that: described A:B=2.5:2.75, temperature of reaction is 60 DEG C, and the reaction times is 2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310140958.6A CN103232412B (en) | 2013-04-22 | 2013-04-22 | One prepares the method for 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310140958.6A CN103232412B (en) | 2013-04-22 | 2013-04-22 | One prepares the method for 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103232412A CN103232412A (en) | 2013-08-07 |
| CN103232412B true CN103232412B (en) | 2016-02-10 |
Family
ID=48880493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310140958.6A Expired - Fee Related CN103232412B (en) | 2013-04-22 | 2013-04-22 | One prepares the method for 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103232412B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2461460A (en) * | 1949-02-08 | N-acixphenothiazines | ||
| CN1086825A (en) * | 1992-08-31 | 1994-05-18 | 弗·哈夫曼-拉罗切有限公司 | Three ring and tetracyclic compounds |
| WO2011153331A2 (en) * | 2010-06-02 | 2011-12-08 | The General Hospital Corporation | Optical sensor conjugates for detecting reactive oxygen and/or reactive nitrogen species in vivo |
-
2013
- 2013-04-22 CN CN201310140958.6A patent/CN103232412B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2461460A (en) * | 1949-02-08 | N-acixphenothiazines | ||
| CN1086825A (en) * | 1992-08-31 | 1994-05-18 | 弗·哈夫曼-拉罗切有限公司 | Three ring and tetracyclic compounds |
| WO2011153331A2 (en) * | 2010-06-02 | 2011-12-08 | The General Hospital Corporation | Optical sensor conjugates for detecting reactive oxygen and/or reactive nitrogen species in vivo |
Non-Patent Citations (1)
| Title |
|---|
| Phenothiazine inhibitors of trypanothione reductase as potential antitrypanosomal and antileishmanial drugs;Cecil Chan，等;《J.Med.Chem.》;19980115;第41卷(第2期);第148-156页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103232412A (en) | 2013-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101786948B (en) | Method for preparing 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone | |
| CN110590819A (en) | Process for producing organoboron compound and process for producing beta-hydroxyorganoboron compound | |
| CN110372611B (en) | Method for selectively synthesizing polysubstituted dihydro quinazolinone or quinazolinone | |
| Li et al. | Synthesis of 2, 3, 5, 6-tetrasubstituted pyridines via selective three-component reactions of aldehyde and two different enaminones | |
| CN102702143B (en) | Method for preparing 2-acetylfuran | |
| CN110003011A (en) | It is a kind of using nitrate as the preparation method of the nitroolefin derivative in nitro source | |
| CN103232412B (en) | One prepares the method for 4-(N-thiodiphenylamine-)-carbonyl-2-butylene acid | |
| CN109180601B (en) | Organic amine catalyzed CO2Method for synthesizing 2, 4-oxazolidinedione compound | |
| CN107011211A (en) | A kind of preparation method of para-Phthalonitrile | |
| CN108623488B (en) | Synthetic method of aminomethylbenzoic acid | |
| CN113845521B (en) | Method for synthesizing imidazo nitrogen-containing heterocyclic hydrazine derivative by aqueous phase photocatalysis one-pot method | |
| CN105085582B (en) | Different part cyclopentadienyl titanium complex crystal and its application in β aminocarboxyl compounds are prepared | |
| CN103288774B (en) | Method for preparing 2-(carbonyl-N-phenothizainyl)-benzoic acid | |
| CN112341475B (en) | Preparation method of clopidogrel hydrogen sulfate | |
| CN106349125B (en) | Utilize the method for manganese salt selectivity synthesis (E) vinyl sulfone compound | |
| CN105237466B (en) | A kind of method for synthesizing three substituted pyridine derivatives | |
| CN102000605A (en) | Cuprous catalytic initiator Cu2(L)Cl2, preparation method thereof and preparation method of N-heterocyclic aromatized product | |
| CN113651720B (en) | Substituted alkenyl thiocyanate compound and preparation method thereof | |
| CN105153421B (en) | One kind prepares tetramethyl piperidine nitrogen oxygen free radical polymer process | |
| CN104910090B (en) | Dihydro-isoxazole class compound and its synthetic method | |
| CN116462619B (en) | Preparation method of cyclopentenone derivative | |
| CN102127032B (en) | Method for synthesizing poly-substituted 5-acyl-2-imine thiazoline | |
| CN114213350B (en) | Preparation method of statin drug intermediate | |
| CN103787991B (en) | Yb/NaY molecular sieve catalyst catalyzes and synthesizes the method for quinoxaline compound | |
| CN107383023A (en) | A kind of 6 (2 methylene quinoline) tryptamines ketone compounds and its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160210 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |